CN102533327A - Single-stage inferior gasoline fraction hydrotreatment process method - Google Patents
Single-stage inferior gasoline fraction hydrotreatment process method Download PDFInfo
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- CN102533327A CN102533327A CN2010106104701A CN201010610470A CN102533327A CN 102533327 A CN102533327 A CN 102533327A CN 2010106104701 A CN2010106104701 A CN 2010106104701A CN 201010610470 A CN201010610470 A CN 201010610470A CN 102533327 A CN102533327 A CN 102533327A
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Abstract
The invention discloses a single-stage inferior gasoline fraction hydrotreatment process method, which comprises the following steps of: (1) directly mixing an inferior gasoline fraction raw material and recycle oil-recycle hydrogen heated by a heating furnace in a step (3), making the temperature of the mixture reach temperature required by the inlet of a hydrotreatment reactor, and introducing into the hydrotreatment reactor for desulfurization reaction, denitrification reaction and olefin saturation reaction; (2) introducing reaction effluent of the hydrotreatment reactor into a separation system, separating hot recycle oil from the reaction effluent without temperature reduction, and separating the hydrogenated gasoline fraction and gas phase through temperature reduction, wherein the gas phase is taken as recycle hydrogen; and (3) mixing the recycle hydrogen and the hot recycle oil in the step (2), heating in the heating furnace, recycling to the step (1), mixing with the inferior gasoline fraction raw material, and introducing into the hydrotreatment reactor. Compared with the prior art, the method can effectively solve the problem of coking of an inferior gasoline fraction hydrotreatment device.
Description
Technical field
The present invention relates to a kind of inferior patrol cut fraction hydrogenation treatment process method, particularly improve the single hop inferior patrol cut fraction hydrogenation treatment unit method in fortune cycle.
Background technology
Along with crude oil constantly becomes improving constantly of heavy and the level of crude oil processing; The status that is processed in the oil refining process of heavy oil product becomes more and more important; Delay coking process is simple because of technology, investment is low, more and more becomes the important means that oil refining enterprise is handled residual oil, improved yield of light oil.The main liquid product coking distillate of delay coking process comprises coking naphtha and coker gas oil.Because foreign matter contents such as coking distillate unsaturated hydrocarbons, sulphur, nitrogen are all higher; And stability is poor; Be difficult to charging as subsequent processing; Must can be used as feed ethylene, synthetic ammonia material after improving its stability and removing impurity widely, reform and expect and chemical industry light oil use and vehicle fuel etc. through unifining.
Catalytic cracking also is one of important means of heavy oil and residual oil deep processing, be that with the key distinction of delayed coking the raw material that catalytic cracking is handled is better than processing raw material of delayed coking, or raw material carries out hydrogenation pre-treatment etc.Similar with delayed coking, the product that catalytic cracking process obtains such as gasoline fraction, diesel oil distillate etc. have unsaturated hydrocarbons content height, contain impurity such as a certain amount of sulphur, nitrogen simultaneously.
In the industrial production, the gasoline fraction that also has some thermal cracking process to obtain also has above-mentioned similar character.Gasoline fractions such as above-mentioned coker, catalytically cracked gasoline cut, pyrolysis gasoline cut are second-rate, are referred to as the inferior patrol cut in this patent.
Industrial application shows, one of subject matter that perplexs the running of inferior patrol cut fraction hydrogenation device for a long time is to raise and compelled the shut-down in the hydrogenation catalyst bed lamination difference SP, and its major cause is due to the polyreaction that causes of the diolefine in the raw oil.Materials such as the rare hydrocarbon in the raw material, two rare hydrocarbon are when temperature is higher; Be prone to take place Diels-Alder cyclization and polyreaction formation macromolecular organic compound; And further condensation green coke; These green coke reactions mainly concentrate on positions such as high-temperature heat-exchanging, process furnace and reactor head, cause production unit to need frequent shutdowns to handle, and cause to ordinary production to have a strong impact on.
Existing inferior patrol heats up in a steamer in the hydrogen addition technology; A general reactor drum or two tandem reactors of adopting, reaction temperature in generally at the hydrogenation activity of competence exertion catalyzer more than 220 ℃, take off the impurity reaction to reach effective hydrogenation; Add the bigger temperature rise (can produce the temperature rise about 140 ℃) that hydrogenation reaction produces like the coker hydrogenation; Be easy to make the diolefine generation coking reaction in the raw material, the blocking catalyst bed increases reactor pressure decrease; Device running period is shortened in the processing of need stopping work when serious greatly.In general, reaction high temperature elute need with the raw material heat exchange to reclaim and to utilize heat, in interchanger and process furnace, the diolefine in the coking naphtha raw material etc. also is easy to coking, the initial stage can be reduced heat exchange efficiency, the later stage processing of need stopping work.Along with the device prolongation of runtime, quality product descends and can only compensate through improving reactor inlet temperature, causes the aggravation of beds top diolefine condensation green coke, causes reacting system pressure to fall rising, influences the long-term operation of device.Though interchanger and furnace outlet temperature of charge are also not really high, heat exchanger wall and furnace wall temperature are very high; Stove hall temperature like common hydrogenation unit process furnace can reach 500 ℃; High can reach more than 600 ℃, and therefore, the coking problem of interchanger and process furnace is very serious.Sometimes the green coke material can get in the reactor drum with following of material in interchanger and the process furnace, is deposited on reactor catalyst bed top, has further accelerated the obstruction speed of reactor catalyst bed.
How effectively eliminating the coking problem of inferior patrol cut in hydrotreater, is to improve inferior patrol to heat up in a steamer the hydrogenation unit key point of running period.
CN1109495A discloses a kind of Rifining method for catalylic cracking gasoline by adding hydrogen, and described is that hydrogenation and removing diolefine under more shallow hydroconversion condition is to guarantee less loss of octane number with the pre-sulfide catalyst series connection of two different activities and variable grain diameter.Because two kinds of catalyzer can be put into a reactor drum or two reactor drums, can not guarantee that catalyzer reacts under lower temperature of reaction, therefore can not delay raw material and generate oil heat exchanger shell side and heating furnace tube coking degree.
US4,113,603 reports use two sections hydrofinishing process to handle diolefine and sulfide in the pyrolysis gasoline, and the catalyzer of first section nickeliferous-tungsten of use is removed mercaptan, and second section is used precious metals palladium catalyst to remove diolefine, and technology is comparatively complicated.Because the not anti-sulphur of noble metal catalyst, and temperature of reaction is very low, is inappropriate for coking naphtha hydrogenation technique process.
CN1084547A has introduced a kind of hydrodesulfurizationof of naphtha dechlorination dearsenification and the saturated process for purification of aromatic hydrocarbons.Though can aromatic hydrocarbons be reduced to less than below 1%, because dearomatization catalyst is nickel or noble metal catalyst,, must adopt two-stage method technology for preventing the catalyzer sulfur poisoning, flow process is complicated, and operational condition is comparatively harsh.
CN200710012091.0 discloses a kind of method that improves running period of hydrogenation plant for poor petroleum naphtha; Before process furnace, set up a reactor drum; Inferior naphtha at first carries out selectivity diene hydrogenation reaction under lower temperature of reaction, and then carrying out hydrogenation reaction through main reactor, to remove sulphur, nitrogen impurity and alkene saturated.The charging of first reactor drum of this method need be warming up to required temperature in interchanger; Though first reactor inlet temperature is lower; But the very high (temperature of second reactor outlet material of the heat transfer tube wall temperature of interchanger; Generally can reach more than 300 ℃), therefore still there is the problem of interchanger coking.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of single hop inferior patrol cut fraction hydrogenation treatment process method, and the inventive method can effectively solve the coking problem of hydrotreater, prolongs the running period of hydrotreater.
Single hop inferior patrol cut fraction hydrogenation treatment process method of the present invention comprises the steps:
(1) the inferior patrol feedstock is directly mixed with the middle turning oil-recycle hydrogen through the process furnace heating of step (3); It is temperature required that the temperature of mixture reaches the hydrotreating reactor inlet, gets into hydrotreating reactor and carry out desulphurization reaction, denitrification reaction and rare hydrocarbon saturated reaction;
(2) the hydrotreating reactor reaction effluent gets into separation system, and reaction effluent is at first isolated thermal cycling oil without cooling, and gasoline fraction and the gas phase after the hydrotreatment isolated in cooling then, and gas phase is mainly hydrogen as recycle hydrogen;
(3) recycle hydrogen in the step (2) and thermal cycling oil are mixed into and are circulated to step (1) after the process furnace heating and are mixed into hydrotreating reactor with the inferior patrol feedstock.
In the inventive method step (1), turning oil is that over point is 350～480 ℃ the hydrorefined petroleum fractions of process, like the vacuum distillate after the unifining, lubricant base, hydrocracking tail oil (being the hydrogen cracking unconverted oil) etc. after the unifining.Mix preceding inferior patrol feedstock temperature with turning oil-recycle hydrogen and can in cryogenic heat exchanger, heat exchange be warming up to 80～170 ℃; Then with heating after turning oil-recycle hydrogen be mixed to the required temperature of hydrotreatment reaction; The required temperature of hydrotreating reactor inlet is according to the performance of catalyzer; Be generally 210～250 ℃, because reaction temperature rising is bigger, average reaction temperature is generally 280～350 ℃.
The temperature of the turning oil-recycle hydrogen in the step (3) after the heating is confirmed as required, is generally 350～520 ℃, is preferably 370～490 ℃.The consumption of turning oil suits to adjust according to the temperature of reaction needs.When turning oil-recycle hydrogen and raw materials mix, be preferably under the abundant agitation condition and mix, avoid non-uniform temperature.
In the hydrotreating reactor, hydrogen and raw material (the not containing turning oil) volume ratio (hereinafter to be referred as hydrogen-oil ratio, down together) under standard state is 100: 1～800: 1.The volume space velocity during liquid of hydrotreatment reaction (in the inferior patrol feedstock, down with) is generally 1～5h
-1, reaction pressure is generally 1～10MPa.Concrete processing condition can require concrete definite according to raw material oil and quality product.
In the inventive method, the catalyzer that uses in the hydrotreating reactor can be a hydrogenation catalyst conventional in this area; It generally is carrier with the aluminum oxide; With among W, Mo, Ni, the Co one or more is active ingredient, and when catalyzer used, active ingredient was generally sulphided state.The catalyst activity component concentration that uses in the hydrotreating reactor (in the oxide weight of active ingredient) is generally 15%～50%.Catalyzer can use suitable commercial catalyst, also can prepare by prior art.
In the inventive method, in the step (2), separation system can be confirmed by the conventional knowledge in this area, is generally reaction effluent and carries out gas-liquid separation without the direct gas-liquid separator that gets into of cooling, and liquid phase mainly is a turning oil, recycles after the heating.Gas phase is separated through the laggard stepping promoting the circulation of qi liquid of cooling, and this moment, isolated gas phase was mainly hydrogen, as looping back hydrogenation unit after the recycle hydrogen heating; This moment, isolated liquid phase was mainly the gasoline fraction behind the hydrogenation, can after suitable processing, discharge as product.
In the inventive method, hydrogen make-up required in the hydrogenation reaction system can add in the reactive system at arbitrary steps, as adding in the hydrotreating reactor, also can add in the recycle hydrogen.
Compared with prior art, the inventive method has the following advantages:
(1) cancellation high-temperature heat-exchanging directly mixes raw material with thermal cycling oil, because temperature is even; Mixing time is very short; Solve the coking problem when adopting heat-exchange equipment, avoided in the interchanger coking electrodeposition substance or got in the reactor drum depositing, improved Btu utilization efficient simultaneously.
(2) process furnace reacting by heating raw material has not further reduced the problem of the generation of rare hydrocarbon coking in the raw material.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
Below in conjunction with preferred embodiment the present invention is further specified, should be appreciated that preferred embodiment described herein only is used for explanation and explains the present invention, and be not used in qualification the present invention.Embodiment adopts laboratory miniature constant temperature fixed-bed reactor, and turning oil is the vacuum distillate after the unifining.
Table 1 raw oil character
| The raw oil title | Coker |
| Density (20 ℃), gcm -3 | 0.7210 |
| The boiling range scope, ℃ | 40～200 |
| Sulphur content, wt% | 0.79 |
| Nitrogen content, wt% | 0.02 |
| Diolefine, g-I 2/100g | 4.8 |
| The bromine valency, gBr.100g -1 | 71.0 |
| Aromatic hydrocarbons, v% | 9.8 |
Table 2 turning oil character
| The turning oil title | The unifining vacuum distillate |
| The boiling range scope, ℃ | 390～550 |
| Sulphur content, μ g/g | ＜1 |
| Nitrogen content, μ g/g | ＜1 |
The main composition and the character of table 3 catalyzer
| Catalyzer | Hydrotreating catalyst |
| Catalyzer is formed | |
| MoO 3+NiO/wt％ | 25 |
| Carrier | Aluminum oxide |
| The main character of catalyzer | |
| Specific surface, m 2/g | 220 |
| Pore volume m l/g | 0.42 |
Table 4 embodiment processing condition
| Processing condition | |
| The turning oil consumption, raw material weight % | 30 |
| Turning oil-recycle hydrogen temperature after heating, ℃ | 480 |
| Pressure, MPa | 4.0 |
| Hydrogen to oil volume ratio | 600∶1 |
| Volume space velocity, h -1 | |
| Hydrotreating reactor | 1.0 |
| Temperature, ℃ | |
| Raw material heat exchange temperature | 120 |
| Hydrotreating reactor temperature in (calculated value) | 220 |
| The hydrotreating reactor medial temperature | 310 |
Table 5 embodiment test-results
Can find out that from the embodiment data through experiment in 2000 hours, the result of the inventive method still had higher level, particularly problem of pressure drop and obtained good solution.
Claims (10)
1. a single hop inferior patrol cut fraction hydrogenation treatment process method is characterized in that comprising the steps:
(1) the inferior patrol feedstock is directly mixed with the middle turning oil-recycle hydrogen through the process furnace heating of step (3); It is temperature required that the temperature of mixture reaches the hydrotreating reactor inlet, gets into hydrotreating reactor and carry out desulphurization reaction, denitrification reaction and rare hydrocarbon saturated reaction;
(2) the hydrotreating reactor reaction effluent gets into separation system, and reaction effluent is at first isolated thermal cycling oil without cooling, and gasoline fraction and the gas phase after the hydrotreatment isolated in cooling then, and gas phase is mainly hydrogen as recycle hydrogen;
(3) recycle hydrogen in the step (2) and thermal cycling oil are mixed into and are circulated to step (1) after the process furnace heating and are mixed into hydrotreating reactor with the inferior patrol feedstock.
2. according to the described method of claim 1, it is characterized in that: in the step (1), turning oil is that over point is 350～480 ℃ the hydrorefined petroleum fractions of process.
3. according to claim 1 or 2 described methods, it is characterized in that: turning oil is vacuum distillate, the lubricant base after the unifining or the hydrocracking tail oil after the unifining.
4. according to the described method of claim 1; It is characterized in that: the inferior patrol feedstock temperature heat exchange in interchanger before mixing with turning oil-recycle hydrogen is warming up to 80～170 ℃, then with heating after turning oil-recycle hydrogen be mixed to the required temperature of hydrotreatment reaction.
5. according to claim 1 or 4 described methods, it is characterized in that: the required temperature of hydrotreating reactor inlet is 210～250 ℃.
6. according to the described method of claim 1, it is characterized in that: the average reaction temperature of hydrotreating reactor is 280～350 ℃.
7. according to the described method of claim 1, it is characterized in that: the temperature of the turning oil-recycle hydrogen after the heating is 350～520 ℃, is preferably 370～490 ℃, and the consumption of turning oil suits to adjust according to the temperature of reaction needs.
8. according to the described method of claim 1, it is characterized in that: in the hydrotreating reactor, hydrogen and the raw material volume ratio under standard state is 100: 1～800: 1, and volume space velocity is 1～5h during the liquid of hydrotreatment reaction
-1, reaction pressure is 1～10MPa.
9. according to the described method of claim 1, it is characterized in that: the catalyzer that uses in the hydrotreating reactor is a carrier with the aluminum oxide, is active ingredient with among W, Mo, Ni, the Co one or more, and when catalyzer used, active ingredient was a sulphided state.
10. according to claim 1 or 9 described methods, it is characterized in that: the catalyst activity component concentration that uses in the hydrotreating reactor counts 15%～50% with the oxide weight of active ingredient.
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| CN2010106104701A CN102533327A (en) | 2010-12-23 | 2010-12-23 | Single-stage inferior gasoline fraction hydrotreatment process method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974792A (en) * | 2014-04-01 | 2015-10-14 | 中国石化工程建设有限公司 | Fluidized bed hydrogenation system and hydrogenation method |
| CN114763494A (en) * | 2021-01-13 | 2022-07-19 | 中国石化工程建设有限公司 | System and method for hydrofining of coker gasoline |
-
2010
- 2010-12-23 CN CN2010106104701A patent/CN102533327A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104974792A (en) * | 2014-04-01 | 2015-10-14 | 中国石化工程建设有限公司 | Fluidized bed hydrogenation system and hydrogenation method |
| CN114763494A (en) * | 2021-01-13 | 2022-07-19 | 中国石化工程建设有限公司 | System and method for hydrofining of coker gasoline |
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Application publication date: 20120704 |